Utilization of hydrocarbons



are 19, W46, M. s. TAGGART, JR 2,396,909

UTILI ZATION OF HYDROCARBONS Filed March 9, 1942 BY WM ATTORNEY Paienie ar. 19, 1946' 2.396.900 UTHJZATION or ROCARBONS Itflllard S. Taggart, Jan, Houston, 'llex., assignor to Standard (iii Development Company, a corporation of Delaware Application March 9, 1942, Serial No. 433,923

7 Claims.

The present invention is directed to a method for the utilization of hydrocarbons, particularly those gaseous hydrocarbons which react with dimculty and, therefore, have hitherto been useful primarily as fuel.

It is' quence, this gas is ordinarily burned in the open air. This constitutes very considerable'waste of natural resources which has presented a problem to the oil industry for many years.

In addition to the natural source of these by drocarbon gases, there'is the refinery source. In practically all cracking processes, or other processes involving hydrocarbon conversion, there are produced large quantities of fixed hydrocarbon,

gases, which always represent a loss. Ordinarily, for want of a better outlet, these gases are burned for fuel in the refinery operations.

The present invention is based on the discovery that hydrocarbons of the parafiinic type can be converted by bacterial action into useful products. There are a number of bacteria, which may be referred to generally as Bacillus pamflinicus, of which Bacillus methrmicus and Bacillus ethanicus may be mentioned as examples, which have the property of consuming hydrocarbons. (See U. S. Patents 2,269,889, issued January 13, 1942, to L. W. Blau, and 2,294,425, issued September l, 1942, to R. T. Sanderson.) It was originally assumed that these bacteria, in consuming hydrocarbons, converted them into carbon dioxide and water. It has been found, however, that under suitable conditions the action of the bacteria results in the synthesis from these light hydrocarbons of oxygenated organic compounds of various molecular weights, from low boiling alcohols to waxy acids, esters and alcohols. When the reaction is permitted to proceed to completion the product is predominately a heavy waxy body composed of fatty acids and esters thereof, which may be readily saponified.

These hydrocarbon consuming bacteria are aerobic in character, so that it is necessary to supply oxygen with the hydrocarbons in carrying out the method of the present invention. The

reaction seems to be accelerated by an increase in pressure, and the formation of the higher bodies is favored by exposing the reaction mass to ultra violet light, The reaction requires the presence of mineral food for the bacteria. These mineral foods are generally selected from the well known plant foods, such as calcium and potassium salts of nitric and phosphoric acids. A suitable salt mixture for the growth of the bacteria is calcium sulfate, magnesium ammonium phosphate and di-potassium phosphate.

It has been found that the presence of minute amounts of heavy metal salts, particularly of the water soluble type, favors the production of the heavy waxy bodies; Since the reaction is ordinarily carried out in an aqueous medium, the desired amount of heavy metal salt may be in corporated by adding to the solution a quantity of heavy metal salt, such as lead sulfide, which has only a slight solubility in water. Among the suitable heavy metal salts may be mentioned various salts of mercury and bismuth, tin, zinc and the like. Care must be taken in the use of these accelerators, since when they are present in more than minute amounts they tend to poison the bacteria.

The present invention may be better understood from the following detailed description of the accompanying drawing in which the single figure is a front elevation in diagrammatic form of one type of apparatus suitable for the practice of the present invention.

Referring to the drawing in detail, numeral l represents a well, which may be a distillate well, producing naphtha and light gaseous hydrocarbons through a producing string 2. This hydrocarbon mixture is usually processed at the surface to separate the distillate from the gaseous hydrocarbons, preferably by a method which leaves the gaseous hydrocarbons substantially at the well head pressure. For the purpose of illustration, vessel 3 may be assumed to represent a treating plant for the separation of the distillate from the gas, the distillate being withdrawn through an outlet 4 and the gas through an outlet 5. It will be understood, of course, that this separating plant may involve a number of pieces of apparatus and a number of process steps, all

I of the present invention.

The outlet 5 discharges into a vessel 6 in which is arranged a plurality of trays I, each provided line 5 a branch line 9, which is supplied with air air may, if desired, be employed in equal molec-- ular proportions with the hydrocarbons. That is to say, the amount of air supplied may be sufficient to provide one molecule of oxygen for each hydrocarbon molecule. It will be appreciated that the nature of the products 'obtained will depend upon the amount of air supplied, among other factors, and that for the production of any given product the optimum\amount of air' to be employed can be readily determined by experiment.

The bubble caps are so constructed as to provide for a substantial layer of liquid on each tray. This liquid will ordinarily be an aqueous solution of certain salts of the type hereinbefore mentioned, inoculated with hydrocarbon consuming bacteria. The bacteria used for the inoculation may be obtained from soil overlying petroleum deposits .by simple extraction with water. This inoculated solution is introduced into the top of the vessel 6 through a'pipe [2 provided with a valve l3. The gas mixture enters the vessel below the bottom tray and moves upwardly through the vessel while the inoculated solution moves downwardly through the vessel and collects in the bottom. An outlet l4, controlled by a valve I5 is connected to the bottom of the vessel at a point below the normal liquid level therein, for the withdrawal therefrom of fluid which has been subjected to the hydrocarbons and which will contain reaction products.

The vessel 6 will be made of suificient height and provided with a sufiicient number of plates to provide a suitable residence time for the reactants. In practice it is preferred to maintain a relatively slow rate of travel of the reacting fluids. For example, the rate of travel of the liquid may be such that any given part of it will remain in the vessel for a period of about an hour. The speed of travel of the gas may be regulated to obtain the greatest consumption of hydrocarbons for a once through operation under the operating conditions employed. It will be understood, of course, that a battery of vessels such pressures are not required, and that the gas 2,396,900 with bubble caps 8. There is connected to the,

far as they are of high molecular weight, will that on the top of the fluid in vessel I! as a scum and 'can be withdrawn through a line 20.

' Any low boiling alcohols formed may. to a certain extent, be carried oil in vaporized form, with the gas leaving the system through line l8. For this reason these gases are passed through a condenser '2l and then into a collection vessel 22,

' has previously been indicated,'may be'passed through additional units like 6, or, if desired, may

earth, or may be used as a fuel.

In the foregoing illustration the method has been described with reference to a gas producing well. It will be apparent, of course, that the source of gas maybe a cracking unit or other processing unit in a refinery. Again, while in the systemv described the operation is carried out under high pressure, it will be understood that I can be introduced into the system at a pressure like 6 may be employed and the hydrocarbon gas passed through them in parallel or in series, preferably with intermediate regulation of the airhydrocarbon ratio in the latter case.

ature. If the atmosphere happens to be cold, the

temperature of the liquid can be regulated by introducing a heat exchanger into the feed line l2.

The outlet line l4 empties into a settler IE, to the bottom of which line I2 is connected for recirculation of the culture medium through the vessel 6. The oxygenated products, at least in so different type of reaction when subjectedto the method of the present invention. These heavier molecules are more or less readily susceptible to conversion to unsaturates bythe withdrawal of hydrogen. Many of the unsaturates so produced are much more valuable than the original parafiins and furthermore are capable of undergobe further compressed and reintroduced into the I,

ing polymerization in situ to produce heavy hydrocarbon molecules.

The nature and objects of the present invention having been thus described and illustrated, what is claimed as being new and useful and is desired to be secured by Letters Patent is:

1. A method for converting normally gaseous parafiinic hydrocarbons into oxygenated organic compounds which comprises contacting said' hydrocarbons in the presence of oxygen with an aqueous solution of plant food inoculated with hydrocarbon-consuming bacteria of the group consisting of Bacillus methanicus and Bacillus ethanicus and recovering from said aqueous solution conversion products of said hydrocarbons.

2. A method according to claim 1 in which the hydrocarbon gases are passed counter-currently through the aqueous solution.

3. A method for converting normally gaseous paraflinic' hydrocarbons into oxygenated organic compounds which comprises passing said ,hydrocarbons counter-currently through a stream of an aqueous solution of plant food inoculated with hydrocarbon-consuming bacteria of the group consisting of Bacillus methamcus and Bacillus etham'cus while subjecting said stream to the actionof ultra-violet light and supplying oxygen for the growth of said bacteria and recovering conversion products of said hydrocarbons from said aqueous stream.

4. A method according to claim 1 in which the action of the hydrocarbon-consuming bacteria asoasco 3 -on the hydrocarbons is conducted underthe infiuence of ultrae-violet light.

5. A method according to claim 1 conducted under superatmospheric pressure.

6. A method according to claim 1 conducted 5 under superatmospheric pressure in the presence of ultra-violetiight.

7. A method for handling the gaseous eifiuent from a gas producing well which comprises subjecting said gas to the action of an aqueous solul was produced after said treatment.

MILLARD S. TAGGART, JR. 

